Textile finishing



rn uaasesaza'lms UNITED i sfrA'rs I I 2.3mm

' mm rmrsnmo Jack :1. "Thurston, Cos cob, com, assignor to 3 acorporation of Maine ldclaims. -This invention relates to the treatingand fin- Oyauamid Company, New York, N. Y.,

application August so, 1941, .v Serial No. 409,112

ishing of textiles and textile-forming materials such as cotton, linen,wool, viscose, silk. cellulose.

acetate, spun rayon and thelika- More particu- .lariy, theinvention-relatesto textile finishing processes, to finishingcompositions and to textiles finished with compositions consisting of'orcontaining higher aikyl guanamines and their al-. dehyde condensationproducts, as will be de-.

scribed.

A wide variety of softening agents, lubricants, creaseproofing agentsand waterproofing agents have heretofore been applied to textile threadsand fibers. The treatment of textiles for these and similar purposessuch as shrinkproofing is known as textile finishing, and the agentsemploy'ed are known as textile finishing agents. I

- soluble in hot mineral spirits, in. glyceride oils and in .xylene,'butare. insoluble or sparingly sol uble in water. As a rule the compoundsof my, invention show increasing solubility in the above solvents withincreasing chain length and .with

is a principal object of the present invention to provide a new class oftextile finishing agents having improved softening, waterproofing andother properties, and to provide new and im-. proved textile finishingprocesses employing such materials. A further important feature of theinvention resides in the provision of cotton, linen, wool, silk,cellulose ester and other yarns, threads or fabrics finished withcompositions containin higher alkyl guanamines and their reactionprodnets and having improved water-resistance and a more desirable hand.

' I have found that the higher allryl guanamines, in which the alkylgroup attached to the 2-carbon atom of the triazine nucleus contains atleast 7 carbon atoms with or without other substituents in addition tohydrogen, possess remarkable properties when applied to textiles of theabove and similar classes. Many of these guanamines, as such, havesoftening and lubricating properties for certain textile fibers, notablycottop, and they also impart water-repellent properties to a markeddegree. Moreover, these waterrepellent properties may be greatlyenhanced by further reaction of the guanamines, either beforecrystalline solids havingrelatively high melting points and goodstability against heat and discoloration. The unsubstituted members ofthe series have melting points in the range of about 7 '75-150 C. whilethe corresponding mono-N-acyl derivatives have much higher meltinpoints. On the other hand the melting points of the N-N'- diacylcompounds are considerably lower than the melting points of thecorresponding unsubstituted guanamine and wide range of comor aftertheir application to the fiber, or both,

pounds of varying physical characteristics is therefore presented by theinvention in its broader aspects. Most of the higher alkyl guanaminesare increased branching of the chain. I

l'he higher alkyl guanamines as a class are compounds corresponding tothe formula m which R is a saturated or unsaturated al phatic or.cycloaliphatic group containing at least 7 carbon atoms attached to thetriazine nucleus by.

a carbon-to-carbon bond. This group may be further substituted byhalogen, hydroxy, alkoxy, oxyaryl, aryloxy, carboxylic, carbonyl,sulfonic, amino, amido or other groups as will be subsequentlyexplained, and any one or more or A, B and X may be H or any othersubstituent such as acyl, alkyl, cycloalkyl, aromatic and the like.

A few representative compounds falling withinthe above definition, andwhich may be applied to textile threads or fibers'to vary the propertiesthereof in accordance with the present invention,

are as follows: J

(1) Representative long chain saturated or unsaturated aliphaticguanamines are octanoflilanamine, decanoguanamine, lauroguanamine,myristoguanamine, palmitroguanamine, stearogu'anamine, oieoguanamine,linoleoguanamine and similar higher alkyl guanamines obtained by thereaction of biguanide or substituted biguanides with vegetal (animal andvegetable) oils, the fatty acids thereof or preferably the methyl estersof these fatty acids such as those obtained from olive oil, hydrogenatedcotton seed oil, coconut oil, teaseed oil, peanut oil and the like.Usually guanamines obtained from saturated higher fattyacids or fromfatty acids having only a limited degree of unsaturation such as oleicacid are pre-- ferred in practicing the invention, as the moreunsaturated compounds are less stable to oxidation and to chlorine fromlaundry bleachs.

(2) Representative branched chain guanamines,

which may be used in practicing the inventionaremethyl-isoamylacetoguanamine, N-acyl acetoguanamines, beta betadi-n-propylpropionoguanamine, di-isobutylacetoguanamine,n-amyin-heptylacetoguanamine, di-n heptyiacetoguanamine,di-n-octylacetoguanainine, ethyl-n-buethyl -isoamylacetoguanavetoguanamine, 4' ethyl 2 octanoguanamine. Representative cycloaliphaticguanamine are those obtained. for example, by condensing naphthenicacids and their aliphatic esters with 'biguanide or substitutedbiguanides and similar condensation products of maleic acid or anhydridewith tung oil and with terpenes, and ortho-\ carboxy-endomethylenetetrahydrobenzoguana- I rupted, for I have found that good results areobtainable with compounds of both types when the radical contains atotal of at least seven carbon atoms. Thus, for example,beta-octadecylamino-propionioguanamine and stearylaminoacetoguanaminepossess softening and waterproofing properties for textiles comparableto those of stearoguanamine, particularly when con- 1 densed withformaldehyde.

Other compounds illustrative of the class of guanamines containingorganic substituents are the higher alkoxyalkyl guanamines such as betaoctadecoxypropionoguanamine and beta amyloxypropionoguanamine. Compoundsrepresentative of other groups that may be. present areomega-carbomethoxygonoguanamines, omega-carboxypelargonoguanaf mine,beta-N dibutylcarbamyl propionoguanamine, alpha-methoxy-beta-Noctylcarbamylpropionoguanamine (CaHrLNHCOCHzCI-I, (on3) camel)beta-carboxy beta amyloxypropionoguanamine and omega-acetylundecanoguanamine.

tion in the presence of alkaline catalysts. Metal alcoholates areparticularly useful for this purpose, and sodium methylate is thepreferred catalyst. The condensation product is usually recovered byfiltration and purified by recrystallization from methanol. otheralcohols, acetone, methylethyl ketone, hot water or other suitable 1solvents. Many of the N-substituted guanamines may also be prepared fromthe corresponding un- 'salts, preferably in the by fusion with aminepresence of a fiux such substituted guanamines as phenol and 'acondensation catalyst such as pelargonoguanamine, omegacarbobutoxypelar-(4) As is pointed out in my copending appli cation Serial No. 409,113,filed concurrently herewith the presence of substituents on one or bothof the amino groups of the guanamines is frequently of advantage intextile treatment, for these substituentsmay modify the solubilitiesofthe compounds and their compatibility with resins, waxes, starches, gumsand other ingredients of textile finishing compositions with which theguanamines may be employed. Representative N-substituted higher alkylguanamines that have been prepared and tested are4-N-phenyl-lauroguanamine, 4-N-butyl-2 (alpha ethyl) hexanoguanamine,4-N-octanoyl-octanoguanamine, 4-N- lauroyl-lauroguanamine, 4--stearoyl-stearoguanamine, 4-N-phenyl-stearoguanamine and disubstitutedderivatives such as 4-N-phenyl-6-N- myristoyl-myristoguanamine and 4,6-N,N'-diacetyl decanoguanamine. I

The above and other guanamines falling within the scope of the inventionmay be prepared by reacting with unsubstituted or substitutedaliphaticand cycloaliphatic carboxylic acids and their esters andhalides. When the acid' halides are used the reaction usually proceedssmoothly upon simple admixture of the reagents in .the presence of inertsolvents, but when the esters are employed it is frequently desirable tocarry out the reac- 'and a permanent laundry-resistant zinc chloride.-N-acyl guanamines may be prepared insimilar manner by heating theunsub-- tituted guanamine with an acid chloride or acid anhydride.

It is an important advantage of the higher alkyl guanamines fallingwithin the scope of the present invention that they will combine withformaldehyde, acetaldehyde, butyraldehyde and other aldehydes to formcondensation products, for it is in this form that they are most usefulas finishing agents for textiles. When dispersible resins are desired itis usually advisable to employ guanamines containing at least tworeplaceable amino hydrogen atoms and to use rather mild conditions forthealdehyde condensation, such as by agitating the aldehyde andguanamine solution at 50-70" C. until the reaction is complete,-and aninert solvent may be used to maintain the guanamine in a dispersed format these temperatures. The resulting resin solutions which are firstformed can usually be diluted with limited quantities of water, but uponcontinued heating or upon reaction at higher temeratures a hydrophobicresin isproduced. Further polymerization is obtained upon heating theresin after its application to the textile fibers,

waterproofing effect is obtained when the fiber is first-impregnatedwith the resin in its water-dispersible stage and then subsequentlyheated to further cure the resin to the watereinsoluble stage.

Although other aldehydes may be employed I prefer to condense theguanamlnes with formaldehyde, which may be used in the form of ordinary3'l% formalin solutions, or as strong aqueous formaldehyde solutions of40-50% strength stabilized by the addition of 4-10% of melamine, or asparaformaldehyde. At least one mole of formaldehyde for each mole ofguanamine should be used, and in the case of N-unsubstituted guanaminesat least two moles of formaldehyde should be employed. When higherformaldehyde ratios of the order of 6-8 moles or more for each mole ofthe guanamine are employed the condensation product is more easilydispersibiguanide or substituted biguanides g ble in water.

The guanamine-formaldehyde condensation products are quite easy toobtain in the form of substantially monomolecular products; that is tosay, as methylol guanamines. When lauroguanamine, stearoguanamlne andother N-unsubstituted long chain guanamines are combined withformaldehyde under the mild conditions described above there is firstobtained a hydrophile syrup. Upon evaporation of the solvent or solventsunder reduced pressure at 30-40 C. methylol guanamines are obtainedwhich are soluble in hot'mineral spirits, hot alcohols and hot xyleneand which can be crystallized from these solvents upon cooling, andwhich are compatible with urea-formaldehyde, melamine formaldehyde andalkyd resins. These compounds can be kylated by heating with primaryalcohols such as methanol, ethanol and butanol in the presence of smallamounts of phosphoric acid, oxalic acid or hydrochloric acid-withazetropic distillation of,

the water of condensation and the resultingzproducts may be applied totextiles from their solutions in organic solvents-as'creaseproofingagents and water-repellents.

Many of the higheralkyl guanaminesare soluble in such organic solventsas acetone, toluene, dioxane and ethers of ethylene glycol and may beapplied as such to textiles as softening agents.

" applying-any ofthe compositions f;

The aldehyde condensation products can alsobe I able excessover. theamountfot. and the ,retention'of'the flnlsh., on"

laundering is thereby gr atiyjn iv As has been stated. above, one' otful methods of preparing textile nesting. containing higher alkyl,guanaminecompounds:

is. with the aid of dispersing agents; 7 Aqtypical procedure of thiskind, which ior tion to textiles, is as follows:

A solution of the higher yr asanrien hyde resin is prepared in methanol;ethanol,

I propanol or other suitable isolventfby iiieating alcohols containingan ethylene oxide ring are also good dispersing agents.

Another class of agents that are particularly well suited for use asdispersing agents are aliphatic and cycloaliphatic substitutedguanamines in which the alkyl radical contains a sulfonic group, such asomega-suli'odecanoguanamine or one or more carboxylic acid groups such'as omega-carboxy-propionoguanamine, omega-carboxy pelargonoguanamine andthe like. These compounds in which the 2-aliphatic or cycloaliphaticsubstituent contains a hydrophilic group may be mixed with the guanamineresins to be solubilized in amounts of 5% to 15% or more, or they may bethemselves reacted with the aidehyde either alone or in admixture withthe other guanamines without losing their water dispersing properties.Another compound which aids in the water dispersal of the higher alkylguanamine resins is the guanamine obtained by condensing biguanide withPetrex, which is a dlene condensation product of pinene with maleicanhydride.

Additional solubilizing and dispersing agents are also described andclaimed in the copending application of Stiegler, Fluck and Thurston,

Serial No. 409,114, filed concurrently herewith. As is pointed out inthat application, such wetting and emulsifying agents as sodisopropylnaphthalene sulfonate, sodium lauryl sulfate, glycerine and otherpolyhydric alcohols, partially or completely neutralized sulfitecellulose liquor, sodium,

' ammonium and ethanolamine stearate, oleate and with agitation. Anaqueous Y dispersion'ofa 3 gum or other suitable binding agent isthenipre-i pared having a concentration suitable for'application to thefiberi for example, a solution of 10-15 parts or-more of water-solubleurea-formaldehyde resin or of methylated methylol melamine in sufilcientwater to make parts. About 5-10 parts by weight ofa 5% solution of asuitable dispersing agent such as sodium isopropyl naphthalene sulfonateis added to this bath and the alkyl guanamine resin solution is pouredin with stirring while maintaining the temperature at about F. Adispersion having an extremely fine particle size is thus obtained, towhich a curing accelerator may be added to speed up the setting of theresin after its application to the fiber if'desired. Four per cent basedon the total resin solids of a mixture of 4 parts hexamethylenetetramine and 30 parts of diammonium phosphate has been used toadvantage. The cloth to be treated is immersed in this bath and thenpassed through squeezing rolls adjusted to a tension such that thequantity of treating solution retained on the cloth is approximatelyequal to the weight of the fabric. The treated cloth is then dried atabout 250 F. and heated for a short time at higher temperatures to curethe resin. A permanent and laundry-resistant waterproof finish isthereby imparted to the cloth.

It should be understood that the above described aqueous dispersion ofhigher alkyl guanamines in admixture with urea-formaldehyde andparticularly methylated melamine-formaldehyde The invention will beillustrated incl-cater detail by the following specific examples, whichshow representative compositions includedthere- 5 in. It should beunderstood, however, that although these examples may describe in detailsome of the more specific details of the invention they are givenprimarily for illustrative purposes tion products to textiles as theprincipal finish ing agent these compounds may be applied in admixturewith resins, gums, balsams and other binders that will give increasedpermanency to the finish. Thus, for example, urea-formaldehyde resins,melamine-formaldehyde resins, phenol-formaldehyde resins, alkyd resinsor any other curing type of resin may be used to assist and theinvention in its broader aspects is not limited thereto. I

- Example 1 Stearoguanamine was prepared by reacting parts by weight ofbiguanide and 300 parts of i was agitated until homogeneous and thenallowed in binding the guanamine to the fiber; These additional bindingagents can be used in considerto stand for about 65 hours, whereupon thepre methyl ethyl ketone and an almost colorless product melting at112-114 C. was obtained. Further purification ,by recrystallization gavea] stearoguanamine melting at 1l6-117 C., but for min m-1. l

the product ofiower' melting point issatisf'actory. I I t Ipecanoguanamine. n-octanoguanamine. '2'- ethylhexanoguanamine, laureanddensation products I myristoguanamine were prepared by substan- I andformaldehyde conwere obtained by agitating with 37% aqueous formalinsolutions at ls-80 c.

' in the ratio ofv 3-8 moles formaldehyde for each mole of the guanaminefor periods of time ,varyt.25 hours 1:03 hours ing from abou dependingtl'iesta'ge of polymerization procedure described in Example 2. Afterheat?- ing at 70 C. for 2.5 hours the thick resin was dried to give asolid which was soluble in arn monia. v

' "Impregnatingbathswere prepared by dissolvf ing the mixed resin'inammonia in varying con- -centrations, and the finish was applied tocotton upon thepH of the solution, the guanamine used; I

product desired, and

whether the formalin was diluted with an orzanic solventv such asmethanol or ethanol. In. the presence of alcohol as a diluent and at pHvalues from about 7.0 to

1-The preparation of 'a stearoguanamine-fonnaldehyde is typical; and isas follows:

mixture of 42 parts by weight of steamguana'mine prepared by the abovedescribed process and imparts of 37% aqueous formaldehyde washeated at70 C. for about 12 minutes with vigorous stirring. As thestearoguanaminebecame warm it softened and emulsified, and after 12minutes the formaldehyde condensation proddehydration. 4

not "was obtained. When the reaction mixture .was cooled with stirringthe resin remainedin the form or a stiff emulsion which could bedispensed in water, but evaporation of the water at 35-40 9.0 thereaction times were much longer than in the absence of the diluent.

i t m 'ried out by agitating the samples in trichlorethyle Percale-andto spun-rayon dress goods. pregnated samples were F. and cured 3 minutesI addition of sewing accelerator to the bath. Boapings were-made usingin: machine for 1 hour I h Drrcleaning tests were'can" ene for minutes.

7 '1% and 10% ofthe finish was applied cot-' The 1% sample, beforeseeping,-

ton percale. possessed a soft hand and a tendency-to repel water; thehand of the 10% sample was somewhat harsher and the fabric showed goodwaterrepelient properties. Both the dry cleaning, and both samplesretained their water-repel'lent properties after these tests. The

results on spun rayon were similar to those on cotton, except that thefinish was livelier.

C. under reduced pressure gave a paste which.

hardened to a soft resin upon cooling and further I Example 2Equimolecular quantities-ofbi guanide and so,- dium but'yl sebacate weredispersed in methanol,

thoroughly mixed, and allowed tostand. for sev-'- eral days untilprecipitation of the condensation product was complete. The solidmaterial was oelerator. 80x80 cotton percaie filtered, washed withmethanol, and dried. The

sodium salt of omega-carboxypelargonoguanae :mine was extracted from thecondensation product with hot water-and precipitated by addition 1 ofmineral-acid to a pH of about 4.0. After purification by solution inalkali and reprecipitation with acid apure product was obtained in the 1form of a white solid melting at 223225' C'.

35 parts by weight of the omega-carboxy- 31% formalin and the mixturewas heated to or t C. with continuous stirring.

original thick mixture became thinner and final-' -After 1.5 hours'thevlyhomogeneous. and upon stopping the agitator after 2 hours of heatingthe intotwo liquid layers.

; water-layer and drying the resin at reduced prespeilent properties.

mixture separated Upon decanting the thin sure a viscous gum wasobtained Wh1Gh'WM 'SOI- ubie in sodium hydroxide. amineand otheralkaliea' I '5 parts by weight of the resin were dissolved in partsofdilute ammonium hydroxide soluticn and cotton cloth was padded in thebath at prepared. The cloth wasthen squeezed until the resin content was5% on the weight of the fiber and then placed in'a mordanting bath ofaluminum sulfate to precipitate the aluminum salt on the fiber. Thecloth was then dried in an oven whereupon it was found to possess goodwater re- Example 3 10 by weight of stearmmine parts ofomega-carboxypelargonoguanamine were and 20 I combined with 46 parts of31% formalin by the ammonia, 1 triethanolby a standard spray test. whichis applied as folresin described I I Example 4 1.5156118 by weight. r

I in Example 1 were dissolved in methanol and emulsified in parts ofasolution containing 10 parts of the methyl ether of .trimethylolmelamine, 0.6 part of isopropyl naphthalene sulfonate and 4.6

Cotton cloth impregnated -with these compositions. dried and cured alsopossessed good water-repellency.

Exempted .The hydrophobic properties of cloth treated'with higher alkylguanamines in accordance withtho present invention were determinedquantitatively dried and cured 10 inches from a horizontal terproofingagent, and then suspended spray nozzle supplied a head of exactly 6feet. The for 1 minute, during which time water are discharged throughthe nozzle, drained for 10 seconds. rolled between pieces of absorbentpaper to remove surface water, and again weighed. The increase in weightis expressed as ion to laundering,

per cent water absorbed. based on the original dry weight of the cloth.In order to measure samples ofv the treated cloth were washed in an 0.5%soap solution at 1". 30 minutes, rinsedand dried, and again subjected tothe spray test. The samples were then dried 5 minutes etjaso'f' at300'F. without the.

0.5% soap solution containing 0.2% of soda ash in an electric washat 1608., followed by. I

1% andthe 10% sample showed good resistance to 'soaping and to thestearoguananiine capryloguanamine instead of A six-inch square of clothtreated with the wais weighed with waterat 10 1''. under cloth issprayed 1 gallons of the resistance of the finwashed again for a totalof 3.5 'hours. The

higher water absorption values of the first spray tests are explained bythe presence of partially reacted resin components and accelerator onthe cloth which would tend to absorb water.

The finished samples of cloth described in mample 4 were subjected tothis test with the following results:

Example 6 An alkyd resin of high acid number (resin A) was prepared bythe simultaneous reaction of 190 parts by weight of phath'alicanhydride, 101 parts of glycerine and 106.5 parts ofcottonseed fattyacids. After reacting these ingredients and holding for the desiredviscosity the acid number of the resin was 60.

An alkyd resin of low acid number (resin B) was prepared by reacting 183parts by weight of phthaiic anhydride, 100 parts of glycerine and 235parts of castor oil at 425-450 F. until a resin having an acid number oi6-3 was obtained. This resin was cut with 115 parts of butanol to 78%solids.

Resin A was cut to 80% solids by the addition of toluene and 67 .5 partsby weight of this 80% solution were taken. 163.5 parts by weight of theresin B solution were addedv and the mixture was warmed to 40 C. andstirred for. about 10 minutes, or until a homogeneous mixture wasobtained. 35 parts by weight 01' the stearogua naminedormaldehyde resinof Example 1 were stirred into 274 parts by weight of a 50% solution ofa butylated urea-formaldehyde resin in a mix= ture of equal parts ofbutanol and xylene and the resulting solution was then added to thealkyd resin solution and the mixture was cooled to 30 C. and stirred foran additional 10 minutes or until the entire mixture was homogeneous incharacter.

An ammonium caseinate solution was prepared in the following manner: 39parts by weight of casein were soaked in 440 parts of water tor -3 hoursat room temperature, or until the casein was sufiiciently swollen, andthe mixture was then heated to 50430 C. to insure uniform hydration.After cooling to 40-50 C. an emmonium hydroxide solution was added inamounts suificient to obtain a uniform dis sion of the casein.Experience with emulsifying agents of this type has shown that amountsof 28% ammonium hydroxide ranging from to 26 parts by weight aresatisfactory for this purpose, the exact amount depending upon the finalpH desired in the finished emulsion. \After all the casein was dissolvedby the ammonium hydroxide solution additional water was added to make atotal of 505 parts by weight.

The mixture of high acid number akyld resin, low acid number alkydresin, butylated ureaformaldehyde resin and stearoguanamine resin wasagitated vigorously at C. and the solution of emulsifying agent wasslowly added. Addition of the entire 505 parts of the emulsifier wasmade over a period of about 40 minutes,

after which agitation of the mixture was continued for an additional 30minutes or until a, completely uniform emulsion was obtained. Thisemulsion was perfectly stable upon storage and could be easily dilutedwith water without separation.

All wool fabric was padded in a sizing bath containing 3 gallons of theabove emulsion to 100 gallons of water. The impregnated fabric was driedunder tension to prevent shrinkage for 7 minutes at 250 F. The driedfabric was found to possess the same softness as that of the originalmaterial, but was much firmer, and possessed good Water-repellentproperties.

Equally good results were obtained when the butylated urea-formaldehydewa replaced by an equal quantity of butylated melamine-formaldehyderesin prepared by condensing melamine with formaldehyde in the ratio ofabout 1:5 in the presence of an excess of n-butanol and heating withdistillation of water until an anhydrous product is obtained.

Example 7 35.4 parts by weight oi phenyl biguanide and 60 parts byweight of methyl stearate were added to a solution of 4.6 parts byweight or sodium in 160 parts of methanol to which parts of the butylether of ethylene glycol (Butyl Cellosolve) had been added. The mixturewas allowed to stand at room temperature for 24 hours after which it wasevaporated to dryness at reduced pressure. The product was extractedwith carbon tetrachloride, the solution evaporated to dry= ness, and thesolids recrystallized from methanol.

The product was a, white crystalline solid which was identified asa-N-phenyl stearoguanamine.

A representative sample of the crystalline prodnot was converted into aresin by reaction with formaldehyde in the ratio of 5 moles oi aldehydefor each mole of the i N-phenyl stearogua namine. The reaction wascarried out by dis-= solving the guanamine in methanol with the additionof heat, adding formaldehyde which had been neutralized to a pH of 8.0and agitating for about minutes at C. The product had a melting point of(ii-65 0., and could be recrystallized from methanol as a definitemethylol guanamine containing 0.6 mole of formalde hyde per mole ofguanamine. The compound was found to be a plasticizer for urea-formaldehyde textile finishing compositions used for creaseproofing purposes,and was suitable for use in. admixture with such compounds Example 8Ethyl beta-octadecoxy-propionate was pre= pared from octadecoxypropionitrile by refluxing the nitrile with concentrated sulfuric acidin the presence of ethanol for 7 hours. The prcdnot was purified byextraction with chloroform and filtration to remove ammonium sulfate andthe filtrate was neutralized with sodium bicarbonate, washed with waterand dried.

A mixture containing 92.5 parts by weight of the ethylbeta-octadecoxy-propionate, 25 parts of biguanlde, 400 parts ofmethanol, and 400 parts of ethanol was stirred at room temperature for15 hours and then allowed to stand for 4 days. The resulting guanaminewas removed by filtration and after recrystallization from acetone wasfound to have a melting point of 108-110" C.

A representative sample of the beta-octade-= coxypropionoguanamlne wasconverted to the methylol compound by reaction with 37% aque ousformaldehyde solution having a pH of 8.2

in the ratio of 6 moles of formaldehyde for each mole of the guanamine.The reaction was carried out in the methanol solution by heating themixture at 70 C. for 45 minutes. The product when dispersed in water byt'e addition of acetic acid was found to be an excellent waterproofingagent for cotton cloth, cellulose acetate cloth, and othertextilefibers.

A textile treatment bath was prepared containing 1.5 parts by weight ofthe above described guanamine resin and 10 parts by weight of alower-primary alcohol-reacted melamine-formaldehyde resin. When cottoncloth was padded in this bath, dried, and cured at suitable temperaturesit showed waterproofing properties comparable to those of the bestwaterproofed cotton fabrics now on the market.

Example 9 16.8 parts of 4-N-octanoyl-ootanoguanamine was stirred into amixture of parts of 37% aqueous formaldehyde neutralized to pH 8 withtriethanolamine, and 100 parts of isopropanol.

The mixture was heated to reflux, 100 parts of butanol were added, andthe refluxing was continued for 40 minutes. After this time theisopropanol was distilled and the product was cooled and filtered toremove a small amount of uncombined guanamine.

- The filtrate was a clear syrup containing 18% of the octanoguanamineresin by weight. 100 parts of this syrup were dispersed in 1000 parts ofan aqueous solution containing 10% of methylated methylol melamine, 5parts of a mixture containing 88% diammonium phosphate and 12% ofhexamethylene tetramine and 6% of sodium isopropyl naphthalenesulfonate. 80 x 80 cotton percale was padded in this solution, dried at250 F. and cured 4 minutes at 300 F., after which treatment it was foundto possess improved softness and water-repellency.

Example 10 Aminoacetoguanamine was prepared by reacting a solution of 70parts by weight of glycine ethyl ester hydrochloride'in 200 parts ofmethanol, 13.8 parts of metallic sodium in 200 parts methanol, and asolution of 60.5 parts of higuanide in 175 parts methanol. The sodiummethylate solution was first added to the glycine ester salt, theresulting sodium chloride filtered off, and the filtrate added to thebiguanide solution.

68 parts by weight of stearyl chloride was dissolved in parts of dioxaneand slowly added to a suspension of 28 parts of aniinoacetoguanamine in200 parts of pyridine while maintaining the temperature below 20 C. Thereaction mixture was allowed to stand for 5 hours and was then refluxedfor one-half hour, after which it was poured into ice water and theproduct recovered and recrystallized. The stearylaminoacetoguanamine soprepared was a light tan solid which softened at 120 C. and wascompletely fused at 174 C. The product was condensed with formaldehyde,using 6 moles of 37% aqueous formaldehyde solution for each mole of thestearylaminoacetoguanamine. The formaldehyde was adjusted to a pH of 8.0and added to a suspension of the guanamine in methanol and the mixturewas heated to 75 C. and agitated at this temperature for 30 minutes. Theresulting resin was applied as a water repellent to spun rayon challis.An emulsion was prepared in the man- 4-5 are mixed with about 100 norpreviously described using 1.5% of the guanamine and 10% of methylatedmethylol melamine, based on the total weight of the solution, and 6% ofcuring accelerator, based on the amount of resin. After drying at 250 F.and curing for 4 minutes at 280 F. the cloth was soaped 30 minutes,rinsed and dried, and subjected to the spray test. It was found thatonly 39.6% of water was taken up by the fabric.

Example 11 123 .parts of 37% aqueous formaldehyde solution having a pHof 8.5 are mixed with parts of ethyl-n-butylacetoguanamine and themixture is heated at 60-100 C. for 1-3 hours, thus producing a clear,aqueous syrup.

58 parts of 37% formalin having a pH of about parts ofethylisoamylacetoguanamine and heated under reflux at 7090 C. for about3 hours, thereby producing a clear aqueous syrup.

100 parts of impure di-n-butylacetoguanamine and 68 parts of 87%formalin having a pH of 4-5 are mixed and refluxed at 60-90 C. until aclear syrup is obtained, requiring about 1-4 hours. Similarly otherguanamines havin branched chain radicals containing at least 7 carbonatoms may be condensed with aldehydes such as formaldehyde in the samegeneral manner as set forth in the above examples. Mixtures of theguanamines with melamine, urea, or mixtures of melamine and urea, whencondensed with formaldehyde or other aldehydes produce resinouscondensation products having desirable properties as the guanaminesappear to exert a plasticizing action on the melamine and ureacondensation products.

The aqueous resinous syrups prepared according to my invention have a"wide variety of applications in the treatment of textiles. They maycellulose derivatives such as cellulose acetate,

cellulose propionate, ethyl cellulose, etc. Dyes, lakes and pigments maybe mixed with my guanamine-aldehyde condensation products and uponheating the mixture, insoluble materials are obtained. Furthermore,dyes, lakes and pigments, may be applied to substrata either before orafter an application of a solution, dispersion or emulsion containing myguanamine-aldehyde condensation products. Upon application of heat, thedyes, lakes, or pigments are affixed to the substrata by means of theinsoluble guanaminealdehyde condensation products.

Generally in .the treatment of textiles, it has been found preferable touse aqueous syrups containing my guanamine-aldehyde condensationproducts and if this be done, various water-soluble adjuncts may beadmixed therewith, e. g., starch, gum tragacanth, the alginates, casein,etc.

Suitable softeners may be included in the com-,

my copending application Serial No. 33d,810, filed April 26, 1940.

What I claim 'is:

l. A method of finishing textiles which com prises the step of applyingthereto a finishing agent containing a water-insoluble guanamine thenheating the textiles to dry and set the finish.

on the fibers.

aliphatic radical containing at least seven carbon atoms, impregnatingthe textiles with said finishing composition, and heating theimpregnated textiles to dry the same and set the finlshon the fibersthereof. I

9. A method of finishing textiles which com= prises the steps ofpreparing a liquid finishing composition comprising an aqueousdispersion of a water-insoluble guanamine in which the 2-car bon atom isconnected by a carbon-to-carbori bond with an aliphatic radicalcontaining at least seven carbon atoms, impregnating the textiles withsaid finishing composition, and heating the impregnated textiles to drythe same and set the finish on the fibers thereof.

10. A method of finishing textiles which com- I prises the steps ofpreparing an aqueous disper- 3. A method of finishing textiles whichcomprises the step of applying thereto a finishing agent containing aformaldehyde condensation product of a water-insoluble guanamine havinga member of the group consisting of aliphatic and cycloaliphaticradicals containing at least seven carbon atoms directly attached to the2-carbon atom thereof by a carbon-to-carbon bond and then heating thetextiles to dry and set the finish on the fibers.

4. A method of finishing textiles which comprises applying thereto'afinishing agent containing a water-insoluble guanamine having a memberof the group consisting of aliphatic and cycloaliphatic radicalscontaining at least seven carbon atoms directly attached to the 2-carbonatom thereof by a carbon-to-carbon bond together with a binder thereforand then subjecting the fibers to heating to set the finishing agent onthe fiber.

5. A method of finishing textiles which comprises applying thereto afinishing agent containing a water-insoluble guanamine in which the 2-carbon atom is connected by a carbon-to-carbon bond with amember of thegroup consisting of aliphatic and cycloaliphatic radicals containing atleast seven carbon atoms together with a curable heat-curing resin otherthan a guanamineformaldehyde resin and then heating the textiles to setthe finishing agent thereon.

6. A method of finishing textiles which comprises applying thereto afinishing agent containing a water-insoluble guanamine in which the 2-carbon atom is connected by a carbon-to-carbon bond with a member 01 thegroup consisting of aliphatic and cycloaliphatic radicals containing atleast seven carbon atoms together with a curasion containing awater-insoluble guanamine in which the Z-carbon atom is connected by acar= bon-to-carbon bond with an aliphatic radical containing at leastseven carbon atoms, said dispersion also containing as an emulsifyingagent a water-soluble guanamine containing an allphatic radical that issubstituted by a member oi the class consisting of sulfonic andcarboxylic acid groups, impregnating the textiles with said dispersion,and heating the impregnated textiles to dry th same and set the finishon the fibers 40 the 2-alky1 roup is a hydrocarbon chain conbleheat-curing alkyd resin and then heating the insoluble guanamine inwhich the Z-carbon atom is connected by a carbon-to-carbon bond with antaining nine to seventeen carbon atoms and then heating the textiles todry and set the finish on the fibers.

13. A method of finishing textiles which comprises the step of applyingthereto a agent containing a formaldehyde condensation product of a2-alkyl ge in which the 2-a1kyl group is a hydrocarbon chain containingat least seven carbon atoms and then heating the textiles to dry and setthe finish on the fibers.

14. A method of finishing textiles which cornprises the step of applyingthereto a finishing agent containing 9. formaldehyde condensationproduct of a Z-alkyl guanamine in which the .z-alkyl group is ahydrocarbon chain containing nine to seventeen atoms and then heatingthe textiles to dry and set the finish on. the fibers.

15. A method of ir textiles which comprises the step of applying theretoa finishing agent containing stearoguanamine and then heating thetextiles to dry and set the finish on the fibers.

16. Textiles characterized by improved waterrepellency and having theindividual fibers there of coated with a cured finishing compositioncontaining a water-insoluble guanamine having a member of the groupconsisting of aliphatic and cycloaliphatic radicals containing at leastseven carbon atoms directly attached to the 2-carbon atom thereof by acarbon te-carbon bond said textiles be lit. been finished by the method01 JACK T. THURSTON.

